Foamed polymeric materials

ABSTRACT

Foamed water-swellable polymeric water absorbent materials are prepared by contacting a polymer capable of having a water-swellable character and containing acid moieties in acid form with a blowing agent such as sodium bicarbonate, which blowing agent is capable of neutralizing the acid moieties of the polymer. The foamed polymers are useful in a wide variety of water absorbent applications.

CROSS-REFERENCE TO RELATED APPLICATION

This is a divisional of application Ser. No. 633,833, filed July 24,1984, U.S. Pat. No. 4,529,739.

BACKGROUND OF THE INVENTION

The present invention relates to polymeric materials, and in particularto those polymeric materials which are employed in the form of a foam.

Water-swellable hydrophilic polymers are useful as absorbents for water.Examples of such polymers and uses, thereof, are disclosed in U.S. Pat.Nos. 3,926,891; 4,190,562; 4,293,609 and 4,424,247. Examples ofdisposable absorbent articles containing water absorbent polymers aredisclosed in U.S. Pat. No. 3,888,257.

It has been common practice to employ high molecular weightwater-swellable hydrophilic polymers in water absorbent applications.Such high molecular weight polymers provide desirable properties such asincreased water absorbency and high gel strengths. Unfortunately, suchhigh molecular weight polymers are extremely viscous and are difficultto formulate.

In view of the deficiencies of the prior art, it would be highlydesirable to provide a process for preparing polymeric materials whichcan be easily formulated for use in applications such as those involvingthe absorption of aqueous fluids.

SUMMARY OF THE INVENTION

The present invention is a process for preparing a foamedwater-swellable polymeric water absorbent material, said processcomprising contacting a polymer capable of having a water-swellablecharacter and containing a functionally effective amount of acidmoieties in acid form, with a blowing agent which is capable ofneutralizing an effective amount of acid moieties.

In another aspect, the present invention is a process for preparing afoamed water-swellable polymeric water absorbent material, said processcomprising contacting a polymer capable of having a hydrophiliccharacter and containing a functionally effective amount of acidmoieties in acid form, with a blowing agent which is capable ofneutralizing an effective amount of acid moieties and said polymer issimultaneously subjected to crosslinking.

In yet another aspect, the present invention is the foamedwater-swellable polymeric water absorbent material which can be preparedvia the processes of this invention.

Surprisingly, the foamed polymeric materials of this invention arehighly porous, highly aerated and can be flexible. The foamed materialsdry quickly, generally having an open cell structure and low density.

The foamed polymeric materials of this invention have a wide variety ofuses. That is, numerous articles can comprise the polymeric materials ofthis invention. Of particular interest are those uses wherein polymericmaterials are used as water absorbent materials.

DETAILED DESCRIPTION OF THE INVENTION

The water-swellable hydrophilic polymers useful in this inventionpreferably can be any of the known hydrophilic polymers that can befoamed as described hereinbefore. Preferred hydrophilic polymers aremost preferably lightly crosslinked or are capable of being lightlycrosslinked. Such hydrophilic polymers include acrylic copolymers,starch/graft copolymers, water-insoluble alkali salt of saponified,gelatinized starch/polyacrylonitrile graft polymers, and the like.Examples of suitable monomers, polymers and crosslinking agents aredisclosed in U.S. Pat. Nos. 3,997,484; 3,926,891; 3,395,099; 4,090,013;4,190,562; 4,405,387. Especially preferred polymers are disclosed inU.S. Pat. Nos. 4,117,184; 4,176,677; 4,293,609; and 4,424,247; which areincorporated herein by reference.

The preferred hydrophilic polymers useful in this invention arepolyelectrolytes exemplary of which are ammonium or alkali metal saltsof homopolymers of acrylic, methacrylic acid, itaconic acid, and thelike, as well as copolymers thereof with one or more ethylenicallyunsaturated comonomers. These polymers contain a functionally effectiveamount of acid moieties in acid form, as is required in the process ofthis invention. Examples of suitable monomers useful in preparingpolymers; polymers and copolymers; crosslinking agents; etc. aredisclosed in the aforementioned U.S. Pat. No. 4,424,247.

Also useful of this invention are polymers comprising polymerizedsulfonate monomers which can be used in place of or in addition to theaforementioned acrylate monomers. Examples of suitable water-soluble,ethylenically unsaturated sulfonate monomers include N-sulfoalkyl,α,β-ethylenically unsaturated amide salts such as the alkali metal saltsof 2-acrylamido-2-methylpropane sulfonic acid, 2-acrylamido propanesulfonic acid, 2-acrylamido ethane sulfonic acid as well as other suchmonomers listed in U.S. Pat. No. 3,692,673 which is hereby incorporatedby reference; alkali metal salts of sulfoalkyl esters of unsaturatedcarboxylic acids such as 2-sulfoethyl methacrylate and other suchsulfoalkyl esters as listed in U.S. Pat. No. 4,075,134 which is alsoincorporated by reference; salts of sulfoarylalkenes such as vinylbenzylsulfonic acid and the various salts of vinylbenzyl sulfonate, p-styrenesulfonic acid, salts of sulfoalkenes such as vinyl sulfonic acid, andthe like. Of the foregoing sulfonate monomers, the sulfoalkylderivatives of acrylamide and methacrylamide are preferred with those ofacrylamide being especially preferred, particularly the sodium andpotassium salts of 2-acrylamido-2-methylpropane sulfonic acid (AMPS),and 2-acrylamido-2-propane sulfonic acid. In the most preferredembodiments, the sulfo group is employed in the form of an alkali metalsulfonate such as sodium sulfonate.

For the purpose of this invention, a moisture absorbent orwater-swellable polymer or polyelectrolyte is one that absorbs severaltimes it weight of an aqueous liquid, preferably more than about 15times its weight in water. The amount of water which a particularpolymer will absorb (i.e., the water absorbent capacity) is dependentupon the pH of the aqueous medium which is being absorbed, the molecularweight of the polymer, the amount of ionic character of the polymer, theamount of crosslinking in the polymer, among other factors. In addition,for purposes of this invention, a polymer capable of having awater-swellable character is that polymer which can be modified (e.g.,by hydrolysis) in order to provide a swellable character.Advantageously, such polymers are lightly crosslinked.

The polymers of this invention require a functionally effective amountof acid moieties in acid form. By this is meant that there is asufficient number of acid moieties pendant from said polymer backbone toprovide a foamed product when said acid moieties are neutralized withsaid blowing agent. If the amount of acid moieties is very small, asmall amount of foaming will occur. Typically, the amount of acidmoieties in acid from varies from about 1 to about 60, preferably fromabout 40 to about 50 weight percent, based on monomers containing acidmoieties which are polymerized to form the polymer.

The blowing agent capable of neutralizing the acid moieties and capableof forming a foamed product is any agent which can provide foam formingbehavior upon neutralization reaction with the acid moieties. Examplesof those agents are those that provide gases such as carbon dioxide uponneutralization with the acid moiety. Suitable examples include sodiumcarbonate, ammonium carbonate, sodium bicarbonate, ammonium bicarbonate,magnesium carbonate, zinc carbonate, and the like.

The process of this invention is performed by contacting the polymer(and optionally crosslinking agent if necessary) with the neutralizingblowing agent under conditions such that neutralization will occur (andunder conditions which crosslinking will occur if crosslinking agent isemployed). This typically requires that the polymer be dispersed in anaqueous medium which contains the neutralizing blowing agent. Thepolymer (and optional crosslinking agent) and neutralizing blowing agentcan be contacted in a reactor under pressure and the foam released, orcan be contacted under multi-feed conditions such that foaming occurs.If desired, the polymer can be simultaneously hydrolyzed. The foamedpolymer is then dispersed in a gaseous medium, such as air, such thatfoam forming gases and excess water are given off.

If desired, the polymer, (and optional crosslinking agent if necessary)and neutralizing blowing agent can be contacted with a hydrolyzingagent. The polymer is then subjected to hydrolysis (and crosslinkingconditions if necessary) while the acid moieties of the polymer areneutralized with the neutralizing blowing agent. Thus, it is possible toperform the process of this invention employing a polymer as a startingmaterial which is in the form of a latex.

The process provides an improved means for providing high molecularweight materials exhibiting high water absorbent capacities and high gelstrengths. Foamed polymeric materials of this invention are low density,highly porous, highly aerated, have an open cell structure, can beflexible and generally dry quickly. The foamed polymeric materials ofthis invention can be applied to various substrates and further dried.

The compositions of this invention can be incorporated into filmlaminates and other such materials as are described, for exammple, inU.S. Pat. Nos. 4,117,184; 4,176,677; 4,293,609 and 4,424,247. Forexample, thoroughly mixed powder/polymer compositions can beincorporated in wicking substrates and treated as described in U.S. Pat.No. 4,293,609. Such materials exhibit high water absorbent capabilities.

The following examples are presented to further illustrate but not limitthe scope of this invention. All parts and percentages are by weight.

EXAMPLE 1

100 g of a latex dispersion in water and having 40 percent solidscomprises a polymer having 75 percent ethyl acrylate polymerized with 25percent methacrylic acid. To this mixture is added with agitation 50 gof an aqueous solution comprising 9.76 g sodium bicarbonate, 2.1 gpolyoxyethylene sorbitan monolaurate surfactant formulation sold asTween®20, and 0.24 g polyamide epichlorohydrin crosslinking agentformulation sold as Polycup®172, and 52 g of an aqueous solutioncomprising 4.65 g sodium hydroxide. The mixture is held under a pressureless than 700 psi until the dispersion is released through an extrusiondie at about 80° C. onto tissue paper.

EXAMPLE 2

A latex dispersion in water having 46.2 percent solids comprises apolymer having 75 percent ethyl acrylate and 25 percent methacrylic acidin polymerized form. To 204.3 parts of this dispersion is mixed 5 partspolyoxyethylene sorbitan monolaurate formulation, and 4.8 partspolyamidepolyimine epichlorohydrin adduct formulation. A slurry of 54.7percent sodium bicarbonate in water is also prepared. The latexdispersion and the sodium bicarbonate slurry are mixed on a 3.6:1 basis.The mixture is agitated in a mixing/pumping device equipped with amixing head and spray nozzel. A spray of the mixture is deposited on aglass plate preheated to 121° C. which is slowly moved under the spraynozzle. A uniform layer of wet, fine celled, foamed polymer is depositedon the glass plate. The glass plate on which the polymer is deposited isplaced in a hot air over at 121° C. for 3 minutes. The essentially dryabsorbent foam polymer shows an absorbent capacity of 31 g of a onepercent sodium chloride aqueous solution per gram of absorbent foampolymer.

What is claimed is:
 1. A foamed, open-celled water-swellable polymericabsorbent material containing a plurality of neutralized acid moietiesprepared by a process comprising contacting a polymer comprising fromabout 40 to about 50 weight percent of monomers containing pendant acidmoieties in acid form which are polymerized to form the polymer, saidpolymer being capable of absorbing more than 15 times its weight inaqueous liquid with an acid-neutralizing blowing agent so as toneutralize an effective amount of the pendant acid moieties.
 2. Aproduct of claim 1 wherein said polymer capable of having awater-swellable character is lightly crosslinked.
 3. A product of claim1 wherein said polymer is in the form of a latex.
 4. A product of claim1 wherein said polymer is simultaneously hydrolyzed.
 5. An articlecomprising the product of claim
 1. 6. The product of claim 1 whereinsaid polymer capable of having a water-swellable character is selectedfrom the group consisting of carboxylic acid and sulfonic acidpolyelectrolytes, polymers and copolymers of acrylic acids and estersand polymers of sulfonate monomers.
 7. The product of claim 1 whereinsaid polymer capable of having a water-swellable character is acopolymer of ethyl acrylate and methacrylic acid.
 8. A foamed,open-celled water-swellable polymeric water-absorbent materialcontaining a plurality of neutralized acid moieties, prepared by aprocess comprising contacting a polymer comprising from about 40 toabout 50 weight percent of monomers containing pendant acid moieties inacid form which are polymerized to form the polymer, said polymer beingcapable of absorbing more than 15 times its weight in aqueous liquidwith an acid-neutralizing blowing agent so as to neutralize an effectiveamount of the pendant acid moieties and simultaneously crosslinking saidpolymer.
 9. A product of claim 8 wherein said polymer capable of havinga water-swellable character is lightly crosslinked.
 10. A product ofclaim 8 wherein said polymer is in the form of a latex.
 11. A product ofclaim 8 wherein said polymer is simultaneously hydrolyzed.
 12. Anarticle comprising the product of claim
 8. 13. The product of claim 8wherein said polymer capable of having a water-swellable character isselected from the group consisting of carboxylic acid and sulfonic acidpolyelectrolytes, polymers and copolymers of acrylic acids and estersand polymers of sulfonate monomers.
 14. The product of claim 8 whereinsaid polymer capable of having a water-swellable character is acopolymer of ethyl acrylate and methacrylic acid.